凝固速度对Mg-Hg阳极材料组织及性能的影响

Mg-Hg合金是一种海水激活动力电池阳极用材料,为提高海水激活电池的各项电化学性能,采用金相显微组织观测、扫描电镜形貌和成分分析、恒电流放电测量电位等方法,重点研究了Mg-6.4%Hg合金在不同凝固冷却速度下,合金显微组织的变化和放电性能的变化.结果表明:合金中的第二相为Mg3Hg相,随炉冷却和铁模空冷铸造合金中,Mg3Hg相分布在晶界上,而采用水冷模铸造时,Mg3Hg相在晶界和晶内同时析出.Mg3Hg相在晶界析出的情况下,发生电化学反应时容易集中溶解,对镁的氧化膜破坏作用很大,对合金的活化作用增强,造成了合金平均电位负移.当冷却速度增加后,Hg在α(Mg)基体中的固溶度增加,使其活化作用不如在晶界析出大,因此,合金平均电位负移较少.     

时效对Mg-9Gd-4Y-1Nd-0.6Zr镁合金强度和耐蚀性的影响

为获得高强耐蚀的Mg-9Gd-4Y-1Nd-0.6Zr合金,采用光学显微镜、扫描电镜、透射电镜和电化学方法等分析了时效工艺对该合金强度和耐蚀性的影响。结果表明峰值时效合金强度很高但耐蚀性差,晶界析出相粗大且分布连续,在腐蚀溶液中镁合金由于析氢,晶界处很容易形成腐蚀通道。同时纳米尺寸的析出相和镁基体微电偶腐蚀很严重。过时效状态合金强度变化不大但耐蚀性显著增强,过时效样品晶内析出相粗大,晶界析出相分布不连续,腐蚀产物在其表面堆积导致腐蚀通道被堵塞,从而使合金耐蚀性显著提高。     

热处理对Al-Mg-Ga-In-Sn合金微观结构和铝水反应的影响

制备不同镁含量的Al-Mg-Ga-In-Sn合金并对其进行固溶和时效热处理，用XRD和SEM分析和观察了显微结构和腐蚀表面，用AFM/SKPFM测量了合金不同晶界相与铝晶粒间的电势差，用排水法测量了在不同水温下合金的铝水反应。结果表明，热处理改变了合金低熔点界面相的种类、形态以及合金晶粒内Mg和Ga含量。热处理态Mg含量低于4%的合金，其中有Mg₂Sn、MgGa、MgGa₂、MgIn界面相；在Mg含量为5%的热处理态合金中出现了Mg₅Ga₂、Mg₂Ga相。在时效态合金晶粒内有MgGa相析出。与相同成分的铸态合金相比，时效态合金中各晶界相与铝基体间的电位差较大。热处理态合金的产氢速率和产氢率，与合金的Mg含量有关。分析了热处理使合金显微结构和晶界相与铝基体间电位差变化的原因，并讨论了热处理对合金铝水反应的影响。     

铸造Al-Zn-Mg-Cu-Zr-Sc合金热处理析出相转变及其对力学性能的影响

目的 为满足高速列车关键部件的轻量化需求,开发高性能铸造铝合金。方法 熔炼铸造了低锌、低镁且含微量钪的Al-5.78Zn-1.63Mg-1.75Cu-0.17Zr-0.22Sc(质量分数)合金,对合金实施了双级均匀化处理及“固溶+时效”(T6)工艺,结合光镜(OM)、X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)及透射电镜(TEM)多种分析测试手段,对比研究合金在铸态、均匀化态及T6处理态下的微观组织特征,重点关注了析出相的演变,并通过室温拉伸性能实验测试合金的力学性能。结果 铸态合金中的析出相以粗大的Mg(Zn,Cu,Al)2相为主,且分布于晶界或枝晶界,在室温拉伸过程中粗大的Mg(Zn,Cu,Al)2相割裂基体,造成合金在弹性变形阶段的脆断,基本无伸长率;双级均匀化处理后,晶界及枝晶间的第二相明显减少,晶内析出了大量的针状相Mg(Zn,Cu,Al)2,而T6处理后,晶内针状相基本消失,时效过程中析出以η''-MgZn2相为主的高密度弥散分布纳米析出相,其平均尺寸为(9.2±0.9)nm,相比于铸态,T6处理后合金的抗拉强度从417 MPa提高到577 MPa,且展现出一定的伸长率。结论 T6处理后合金中析出相由粗大的针状相转变为高密度弥散分布纳米析出相,该析出相可在变形过程中有效钉扎位错,从而提高合金力学性能。     

高锌镁合金化学镀镍磷初始沉积特征的研究

化学镀Ni-P能提高镁合金的耐蚀性.采用金相观察、X射线衍射(XRD)、扫描电子显微镜(SEM)、能谱(EDS)等技术研究了铸态和固溶态Mg-8Zn-4Al合金化学镀Ni-P合金初始沉积的特点.结果表明:由于镁基体中α固溶体,(Al2Mg5Zn2),τ[Mg32(Al,Zn)49]相的组成元素存在差别,造成了相间的电极电位存在差异,初生的镍离子优先在相和τ相上沉积;随后以最先沉积的点为中心向四周扩展,以胞状形式生长;经过固溶的Mg-8Zn-4Al合金组织主要为过饱和α固溶体,相和τ相析出效果不明显,镍离子的初始沉积变得较为均匀,沉积速度有所减缓.     

Mg-5Yb-0.5Zr变形镁合金的显微组织与力学性能

本文利用熔剂保护法制备了Mg-5Yb-0.5Zr合金,并进行了热挤压和热处理,对合金在各种加工状态下的相结构、显微组织和力学性能进行了试验和测试.结果表明,合金由α-Mg和Mg2Yb相组成,铸态组织中的Mg2Yb相聚集在晶界,并在热挤压过程中被破碎起到限制再结晶和弥散强化的作用;合金经热处理后有一定的时效强化效应,析出相为共轭生长的短棒状Mg2Yb颗粒.合金在挤压态的强度最高,T5态热处理可得到良好的综合力学性能.     

铸态Mg-4Al-2Si合金的显微组织与力学性能

采用重力铸造法制备Mg-4Al-2Si(AS42)镁合金,研究了铸态合金的显微组织和室温力学性能。结果表明:铸态AS42合金主要由α-Mg基体、β-Mg17Al12相及Mg2Si相组成;β-Mg17Al12相呈网状和棒状分布于晶界上,粗大的汉字状Mg2Si相沿晶界或穿晶分布,多边形块状Mg2Si相随机分布于基体组织中。铸态合金的硬度为64.5 HV,室温抗拉强度为113.5 MPa,屈服强度为86 MPa,伸长率为4.1%;拉伸断裂形式为准解理脆性断裂。     

高强高韧Mg-8.5Gd-2.0Y-1.0Ag-0.4Zr合金的组织与性能

研究了高强高韧Mg-8.5Gd-2.0Y-1.0Ag-0.4Zr(wt.%)合金的显微组织和力学性能。结果表明,该合金铸态组织细小,主要由α-Mg固溶体、晶界析出相Mg5(GdY)以及分布在晶粒内部的Zr核组成;T4态时晶界析出相基本完全消失,但出现了一些方块相γ;合金具有明显的时效硬化效果,且随着时效温度的提高,合金的峰值时效硬度下降,峰值时间相应缩短。经200℃峰值时效处理后表现出极为优异的室温力学性能,抗拉强度(UTS)和延伸率分别达到396MPa和9.1%,显著的时效强化是该合金具有优异力学性能的主要原因。如此优异的强度和塑性在常规铸造镁合金中是极为罕见的,对于推广镁合金的应用具有重要意义。     

铸态和挤压态Mg-4Sm-Al-0.3Mn-xZn合金微观组织和力学性能研究

本工作通过光学显微镜(OM)、X射线衍射仪(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、拉伸试验机对铸态和挤压态Mg-4SmAl-0.3Mn-x Zn(x=0、1、2、3)(质量分数)合金的微观组织及力学性能进行了研究。铸态、固溶态合金中观察到了Mg-Al-Sm三元析出相,它是一种长条形基面析出相,具有六方结构,其中a=0.556 nm,c=0.521 nm。该相与镁基体的位向关系为:[0001]_(Mg-Al-Sm)‖[0001]_(α-Mg),■_(Mg-Al-Sm)‖■_(α-Mg)。三种元素的原子比为Mg∶Al∶Sm=98.73∶0.71∶0.56。铸态合金中Mg-4Sm-Al-0.3Mn-3Zn合金具有最佳的拉伸性能,其屈服强度、抗拉强度和延伸率分别为96 MPa、138 MPa和7.2%。挤压态合金中Mg-4Sm-Al-0.3Mn-2Zn合金具有最佳的拉伸性能,其屈服强度、抗拉强度和延伸率分别为269 MPa、298 MPa和16%。     

Fe85Ga15多晶在模拟海水中的应力腐蚀行为研究

研究了新型磁致伸缩材料Fe-Ga合金的应力腐蚀性能。采用恒载荷和慢应变速率拉伸(SSRT)试验,结合电化学测试技术,研究了铸态Fe85Ga15多晶在模拟海水中的应力腐蚀。结果表明,开路电位下,模拟海水中薄板光滑试样恒载荷拉伸能够发生低于材料抗拉强度的断裂,且断裂时间明显依赖于外加应力的大小,外加应力愈大,断裂时间愈短。这表明铸态Fe85Ga15合金在模拟海水中能够发生应力腐蚀开裂(SCC),且SCC归一化门槛应力为σscc/σb=0.34。慢应变速率拉伸显示,SCC敏感性在应变速率为5×10-7/s时最大,用强度损失表示为Iσ=(1-σc/σb)×100%=35%。阴极极化升高而阳极极化降低恒载荷SCC断裂时间。这些结果初步表明铸态Fe85Ga15合金在模拟海水中的应力腐蚀为阳极溶解型。     

合金元素对镁合金耐腐蚀性能影响的研究进展

添加合金元素即合金化是改善镁合金性质、性能的有效途径。总结了基础合金元素(Al、Zn、Mn、Zr等)和微量合金元素(Ce、La、Sc、Er、Nd、Y、Sm、Ho、Gd及混合稀土等稀土元素和Ca、Sr等碱土金属元素以及Pb、Sn、Sb、Si、Hg、Ga等)对合金化镁合金耐腐蚀性能的影响,评述了失重法、电化学方法等合金化镁合金耐腐蚀性能的主要研究方法,指出了当前镁合金合金化及耐腐蚀性能研究中存在的问题和发展方向。     

Room-Temperature All-Liquid-Metal Batteries Based on Fusible Alloys with Regulated Interfacial Chemistry and Wetting

Liquid metal batteries are regarded as potential electrochemical systems for stationary energy storage. Currently, all reported liquid metal batteries need to be operated at temperatures above 240 °C to maintain the metallic electrodes in a molten state. Here, an unprecedented room-temperature liquid metal battery employing a sodium–potassium (Na–K) alloy anode and gallium (Ga)-based alloy cathodes is demonstrated. Compared with lead (Pb)- and mercury (Hg)-based liquid metal electrodes, the nontoxic Ga alloys maintain high environmental benignity. On the basis of improved wetting and stabilized interfacial chemistry, such liquid metal batteries deliver stable cycling performance and negligible self-discharge. Different from the conventional interphase between a typical solid electrode and a liquid electrolyte, the interphase between a liquid metal and a liquid electrolyte is directly visualized via advanced 3D chemical analysis. Insights into this new type of liquid electrode/electrolyte interphase reveal its important role in regulating charge carriers and stabilizing the redox chemistry. With facile cell fabrication, simplified battery structures, high safety, and low maintenance costs, room-temperature liquid metal batteries not only show great prospects for widespread applications, but also offer a pathway toward developing innovative energy-storage devices beyond conventional solid-state batteries or high-temperature batteries.     

Electrochemical behaviour of Al–Zn–Ga and Al–In–Ga alloys in chloride media

The influence of Ga content on the electrochemical behaviour of Al–Zn–Ga and Al–In–Ga alloys in chloride acid and acetic acid media was studied. The presence of Ga in concentration greater than 2.5 wt.% causes an open circuit potential (OCP) shifts of Al–Zn–Ga alloys in chloride solution towards more negative values (−1.38 V(SCE)). The OCP for Al–In–Ga alloys in chloride solution varies between −1.62 and −1.73 V(SCE). The anodic behaviour of these ternary alloys can be interpreted in terms of an amalgam mechanism.     

Recovery of gallium and vanadium from gasification fly ash

The Puertollano Integrated Coal Gasification Combined Cycle (IGCC) Power Plant (Spain) fly ash is characterized by a relatively high content of Ga and V, which occurs mainly as Ga2O3 and as Ga3+ and V3+ substituting for Al3+ in the Al-Si fly ash glass matrix. Investigations focused on evaluating the potential recovery of Ga and V from these fly ashes. Several NaOH based extraction tests were performed on the IGCC fly ash, at different temperatures, NaOH/fly ash (NaOH/FA) ratios, NaOH concentrations and extraction times. The optimal Ga extraction conditions was determined as 25 degrees C, NaOH 0.7-1 M, NaOH/FA ratio of 5 L/kg and 6 h, attaining Ga extraction yields of 60-86%, equivalent to 197-275 mg of Ga/kg of fly ash. Re-circulation of leachates increased initial Ga concentrations (25-38 mg/L) to 188-215 mg/L, while reducing both content of impurities and NaOH consumption. Carbonation of concentrated Ga leachate demonstrated that 99% of the bulk Ga content in the leachate precipitates at pH 7.4. At pH 10.5 significant proportions of impurities, mainly Al (91%), co-precipitate while >98% of the bulk Ga remains in solution. A second carbonation of the remaining solution (at pH 7.5) recovers the 98.8% of the bulk Ga. Re-dissolution (at pH 0) of the precipitate increases Ga purity from 7 to 30%, this being a suitable Ga end product for further purification by electrolysis. This method produces higher recovery efficiency than currently applied for Ga on an industrial scale. In contrast, low V extraction yields (<64%) were obtained even when using extreme alkaline extraction conditions, which given the current marked price of this element, limits considerably the feasibility of V recovery from IGCC fly ash.     

Scanning electrochemical microscopy. 48. Hg/Pt hemispherical ultramicroelectrodes: fabrication and characterization

Hg/Pt hemispherical ultramicroelectrodes (UMEs) (25-microm diameter) were prepared either by electrodeposition from a mercuric ion solution or by simple contact of the Pt disk to a hanging mercury drop electrode. The two methods produced equivalent tips. Optical inspection and electrochemical characterization of these Hg tips with methyl viologen, cobalt sepulchrate trichloride, and hexamineruthenium(III) chloride confirm the hemispherical nature of the UME. The scanning electrochemical microscopy approach curves for all three redox couples over a conductive substrate fit theoretical plots for hemispherical electrodes. The numerical solution of the diffusion equations for substrate generation-tip collection (SG-TC) transients for a finite Pt disk and Hg/Pt hemispherical UME are reported and compared to experimental results. A diffusion layer approximation is presented, and diffusion coefficients are extracted from the simulation. The SG-TC results reveal the enhanced sensitivity of hemispherical UME to radial diffusion.     

Scanning electrochemical microscopy. 32. Gallium ultramicroelectrodes and their application in ion-selective probes

Gallium ultramicroelectrodes for amperometric measurements in scanning electrochemical microscopy were fabricated by introduction of liquid Ga into drawn glass micropipets. Cyclic voltammetry of Ru(NH(3))(6)(3+) and the use of this species for SECM imaging is described. Double-barrel micropipet tips with a Ga amperometric electrode and an ion-selective (K(+)) potentiometric probe can also be constructed. This probe was used to image the K(+) activity near a 20-μm-diameter lumen of a glass capillary.     

Kinetic studies of elemental mercury adsorption in activated carbon fixed bed reactor

Activated carbons are suitable materials for Hg(0) adsorption in fixed bed operation or in injection process. The fixed bed tests provide good indication of activated carbons effectiveness and service lives, which depend on the rates of Hg(0) adsorption. In order to correlate fixed bed properties and operation conditions, with their adsorptive capacity and saturation time, Hg(0) adsorption tests were realized in a bench-scale unit, consisted of F400 activated carbon fixed bed reactor. Hg(0) adsorption tests were conducted at 50 degrees C, under 0.1 and 0.35 ng/cm(3) Hg(0) initial concentrations and with carbon particle sizes ranging between 75-106 and 150-250 microm. Based on the experimental breakthrough data, kinetic studies were performed to investigate the mechanism of adsorption and the rate controlling steps. Kinetic models evaluated include the Fick's intraparticle diffusion equation, the pseudo-first order model, the pseudo-second order model and Elovich kinetic equation. The obtained experimental results revealed that the increase in particle size resulted in significant decrease of breakthrough time and mercury adsorptive capacity, due to the enhanced internal diffusion limitations and smaller external mass transfer coefficients. Additionally, higher initial mercury concentrations resulted in increased breakthrough time and mercury uptake. From the kinetic studies results it was observed that all the examined models describes efficiently Hg(0) breakthrough curves, from breakpoint up to equilibrium time. The most accurate prediction of the experimental data was achieved by second order model, indicating that the chemisorption rate seems to be the controlling step in the procedure. However, the successful attempt to describe mercury uptake with Fick's diffusion model and the first order kinetic model, reveals that the adsorption mechanism studied was complex and followed both surface adsorption and particle diffusion.     

Structure,mechanical properties,corrosion behavior and cytotoxicity of biodegradable Mg–X (X = Sn,Ga, In) alloys

As-cast Mg–Sn, Mg–Ga and Mg–In alloys containing 1–7 wt.% of alloying elements were studied in this work. Structural and chemical analysis of the alloys was performed by using light and scanning electron microscopy, energy dispersive spectrometry, x-ray diffraction, x-ray photoelectron spectroscopy and glow discharge spectrometry. Mechanical properties were determined by Vickers hardness measurements and tensile testing. Corrosion behavior in a simulated physiological solution (9 g/l NaCl) was studied by immersion tests and potentiodynamic measurements. The cytotoxicity effect of the alloys on human osteosarcoma cells (U-2 OS) was determined by an indirect contact assay. Structural investigation revealed the dendritic morphology of the as-cast alloys with the presence of secondary eutectic phases in the Mg–Sn and Mg–Ga alloys. All the alloying elements showed hardening and strengthening effects on magnesium. This effect was the most pronounced in the case of Ga. All the alloying elements at low concentrations of approximately 1 wt.% were also shown to positively affect the corrosion resistance of Mg. But at higher concentrations of Ga and Sn the corrosion resistance worsened due to galvanic effects of secondary phases. Cytotoxicity tests indicated that Ga had the lowest toxicity, followed by Sn. The most severe toxicity was observed in the case of In.     

Electrochemical and spectroscopic investigation of the reduction of dimethylglyoxime at mercury electrodes in the presence of cobalt and nickel

Voltammograms (polarograms) obtained from solutions of cobalt and nickel containing dimethylglyoxime (dmgH(2)) are widely used for the trace determination of these metals. Detailed electrochemical and spectroscopic studies on the reduction process observed in the analytically important ammonia buffer media at mercury dropping, hanging, and pool electrodes are all consistent with an overall 10-electron reduction process, in which both the dmgH(2) ligand and cobalt ions are reduced in the adsorbed state: Co(II) + 2dmgH(2) ? (solution) [Co(II)(dmgH)(2)] + 2H(+); [Co(II)(dmgH)(2)] + Hg ? (electrode) [Co(II)(dmgH)(2)](ads)Hg; and [Co(II)(dmgH)(2)](ads)Hg + 10e(-) + 10H(+) → Co(Hg) + 2[2,3-bis(hydroxylamino)butane]. The limited solubility of the nickel complex in aqueous media restricts the range of studies that can be undertaken with this system, but an analogous mechanism is believed to occur. Low-temperature voltammetric studies in dichloromethane at a frozen hanging mercury drop electrode and in situ electron spin resonance electrochemical measurements on more soluble analogues of the dimethylglyoxime complexes are consistent with an initial one-electron reduction step being available in the absence of water. Deliberate addition of water to acetone solutions enables the influence of the aqueous environment on voltammograms and polarograms to be examined. The results of the present study are compared with the wide range of mechanisms proposed in other studies.     

Dental gold alloys with age-hardenability at intraoral temperature

Dental gold alloys with age-hardenability at intraoral temperature were developed. Either 3 or 6 at% Ga, Al, Zn, In, Ni or Pd were added to an equiatomic AuCu alloy and the effect of additives on the low-temperature age-hardenability was examined. Alloys containing Ga, Al or Zn exhibited excellent low-temperature age-hardenability. The hardness of an alloy containing 6 at% Ga or 6 at% Al was doubled in one to ten days by ageing at 37 °C. Pronounced hardening was not demonstrated in an as-cast alloy, but solution treatment for only a few minutes provided enough age-hardenability. The age-hardening rate at low temperature related closely with the melting temperature of the alloy. Experimental gold alloys exhibited electrochemical behaviour similar to that of a commercial Type IV gold alloy. It is therefore concluded that AuCu alloy with added Ga, Al or Zn is expected to have enough age-hardenability and corrosion resistance for clinical use in the oral environment.